Process for producing resins of weather resistance

ABSTRACT

A process for producing an aromatic hydrocarbon resin having excellent weather resistance and heat resistance which comprises separating a fraction containing a certain amount of conjugated diolefin and indene and indene alkyl derivatives from a hydrocarbon fraction having a boiling point of 140.degree.220.degree. C. obtained from thermal cracking of petroleum, then adding Friedel-Crafts type catalysts to said fraction, subjecting to polymerization reaction at -30.degree.-+60.degree. C. for 10 minutes to 15 hours, thereafter decomposing and removing said catalyst and separating unreacted oils and low polymers from the reaction products by evaporation or distillation.

United States Patent Hayashi et al. 1 Apr. 8, 1975 1 PROCESS FOR PRODUCING RESlNS 0F 3.379.663 4/1968 Take i et a1. 260/82 WEATHER RESISTANCE 3.574.792 4/1971 Hayashi 260/82 3.679.626 7/1972 Tanekusa et a1 404/94 1 1 Inventors: lildeo y hi, KHWZlSZIRI; HISatake 3.753.963 8/1973 Hayashi et al. 260/82 S310; Akio Oshima, both of 3.775.381 11/1973 Hayashi et a1. 260/82 Yokohama, all of Japan 3.778.421 12/1973 Hayashi et al. 260/82 [73] Assignee: Nippon Oil Company, Limited,

Tokyo. Japan Primary E.ram inerRonald W. Griffin Filed: g 31, 1973 gnome Agent. or Firm-Ostrolenk, Faber. Gerb &

offen [21] Appl. No.: 393,288

- Related U.S. Application Data [57] ABSTRACT [62] Division of Ser. No. 163.177. July 16, 1971. Pat. No.

A process for producing an aromatic hydrocarbon resin having excellent weather resistance and heat rel l Foreign Application ty Data sistance which comprises separating a fraction con- July 22. 1970 Ja an 45-63563 taining a certain amount of conjugated diolefin and indene and indene alkyl derivatives from a hydrocar- [52] U.S. Cl...... 260/22 CB; 117/124 E; 117/161 K; bon fraction having a boiling point of 140-220 C. 117/161 H; 260/233; 260/285 R; 260/285 A; obtained from thermal cracking of petroleum, then 260/318 M; 260/336 UA; 260/82; 260/9981) adding Friedel-Crafts type catalysts to said fraction. [51] Int. Cl C081 15/42; C09d 3/60; C09d 3/66 subjecting t0 polymerization reaction at 30+60 C. [58] Field of Search 260/82. 22 CB. 28.5 A, for 10 minutes to 15 hours. thereafter decomposing 260/285 R and removing said catalyst and separating unreacted oils and low polymers from the reaction products by [56] References Cited evaporation or distillation.

UNITED STATES PATENTS 2.824.502 2/1958 Rockwell et a1. 404/94 8 2 D'awmg F'gures PROCESS FOR PRODUCING RESINS OF WEATHER RESISTANCE This is a division of applicationSer. No. 163,177, filed July 16, 1971, and now US. Pat. No. 3,778,421.

This invention relates to a process for producing a hydrocarbon resin having excellent weather resistance and heat resistance. as compared with well-known resins, from a thermal cracked petroleum fraction having a boiling point within the range of from 140 C. to 220 C.

In general, petroleum hydrocarbon resins are obtained by-polymerizing liquid cracked petroleum fractions at room temperature, said fractions prepared by thermal cracking of petroleum. In this cases. a cracked petroleum fraction having a wide range of boiling point such as 280 C., 20-l70 C., and 140-280 C. is employed as a raw material. When a cracked petroleum fraction having a boiling point of about 20-l40 C. is used as raw material, the resin obtained is called a non-aromatic hydrocarbon resin because it contains no aromatic ring. Since such a raw material contains a large amount of conjugated diolefins and nonconjugated diolefms, the resin produced has a high degree of unsaturation, so that the weather resistance of the resin is inferior. Therefore, the resulting resin cannot be employed as a coating material which needs weather resistance. particularly. for a light colored coating material. Furthermore, since the resin has a low softening point of 100 C. or below, it is unsuitable for printing ink, which needs a drying property, and for rapid drying coating material.

On the other hand, when a cracked petroleum fraction having a boiling point within the range of 140-280 C. is used for a raw material, the resin produced is an aromatic resin. In this case, the weather resistance of the resin is also inferior, and when the resin is employed in white paint or traffic marking paint for road signs, conspicuous discoloration occurs in a short period. Therefore, it is considered that the resin cannot be used for the uses mentioned above. Accordingly, it is an idea commonly accepted that petroleum hydrocarbon resins have inferior weather resistance.

The latter resin has a softening point of about 130 C. and this softening point is higher than that of the non-aromatic resin. However, when there is required a resin having a higher softening point, a component for elevating the softening point must be added to the raw material and then, polymerization of the mixture thus obtained is carried out.

In the coating material industry, particularly for traffie marking paint, there is needed a petroleum hydrocarbon resin having favorable water and chemical resistance and favorable weather resistance. Furthermore, there is a request for the preparation of a high softening point type petroleum hydrocarbon resin having a softening point of not less than 160 C. for high-grade printing ink in the printing ink industry.

At present, neither need can be satisfed by the presently existing petroleum hydrocarbon resins.

It is an object of the present invention to provide a process for producing a weather resistant resin sufficiently applicable for the practical use as a resin for traffic paint.

A further object of the present invention is to provide a process for concurrently producing a weather resistant resin sufficiently applicable for the practical use as a resin for traffic marking paint with a high softening point of 160 C. and above which is requested in printing ink industry.

As a result of the detailed study of the present inventors as to the characteristic features of components in a raw material oil, it was found that by strictly separating specified components in the raw material oil as described hereinbelow; the weather resistant resin and high softening point type resin can be obtained from fractions 1 and 11, respectively. The present inventors have further continued the study and development, and thus the process of the present invention has been accomplished. i

The process according to the present invention is carried out as described hereinbelow. A fraction of a thermal cracked petroleum fraction having a boiling point within the range of from -220C. (unsaturated compounds contained therein are substantially styrene and its derivatives, indene and its derivatives), is employed as a starting material, and the starting material is subjected to distillation. A fraction which satisfies a condition such that the content of conjugated diolefin is 0.7 weight percent and below, the rate of conjugated diolefin content is 3 7r or less, the total content of indene and its alkyl derivatives is 2 weight percent or less and the rate of indene content is not more than 8 percent is obtained.

Said fraction is subjected to polymerization by employing Friedel-Crafts type catalyst. The catalyst is removed, and thereafter, unreacted pertoleum fraction and low molecular polymer are eliminated by evaporation or distillation, whereby a hydrocarbon resin having excellent weather resistance is produced.

According to this invention, weather resistant resin for traffic paint and a resin having high softening point of C. and above can be produced concurrently. That is, a fraction of a cracked petroleum fraction obtained by thermal cracking of petroleum having a boiling range of from 140 C.220 C. (unsaturated compounds contained therein are substantially styrene and its derivatives, indene and its derivatives) is employed as a starting material, and the starting material is separated by a series of operations into fractions 1 and 11 which satisfy the undermentioned conditions, respectively. Fraction 1 satisfies a condition such that the content of conjugated diolefin is 0.7 weight percent or less, the rate of conjugated diolefin content is 3 percent or less, the total content of indene and its alkyl derivatives is 2 weight percent or less, and the rate ofidene content is 8 percent or less. Fraction ll satisifes a condition that the total content of indene and its alkyl derivatives is 20 weight percent or more and the rate of indene contenet is 30 percent or more.

The fractions 1 and 11 are subjected to polymerization by employing Friedel-Crafts type catalyst, respectively. Then, the used catalyst is removed, and thereafter, unreacted fraction and low molecular polymer are eliminated by evaporation or distillation, whereby a hydrocarbon resin having excellent weather resistance and heat resistance and a high softening point type hydrocarbon resin having a softening point of 160 C. and above are produced from the fractions 1 and 11, respectively.

The term a series of operations" used herein means that in a process for separating fraction 1 from fraction 11, both of them satisfying the above determined conditions, respectively, from the raw material oil, its operations carried out in such a manner that no intermediate fraction between the fraction 1 and the fraction 11 substantially exists. This is one of the necessary conditions of the present invention.

The starting raw material oil employed in this invention is a cracked petroleum fraction having a boiling range of 140-220 C. found in the by-products obtained when ethylene, propylene, butene, and butadi- TABLE 1 In order to produce a hydrocarbon resin having a good weather resistance and heat resistance in the proccss according to this invention, it is an essential condition that the fraction having a boiling point within the 5 range of 140-220 C. be distilled and a fraction satisfying the following conditions obtained and that said fraction is employed as a raw material oil.

THE FRACTION a. The total content of cyclopentadiene and methylcyclopentadiene. that is, the content of conjugated diolefin in the fraction separated from the above mentioned starting raw material oil is adjusted to a value of 0.7 weight percent or less and the rate of content of the Components in Cracked Oil of l220 C. Fraction Boiling Point Examples of C. (760 mm Content Name of Component Hg abs) (wt. 7r)

Styrene 145.8 1 3-20 Allylbenzene 156-157 0.1-1

-Methylstyrene 165.4 0.5-6

-Methylstyrene 175 05-6 p-Vinyltoluene 168 m-Vinyltoluene 169} 10-20 o-\ "in \'ltoluene 171 lndene 182.2 2-1 1 Methylindene homologs 184-206 Dimethylindene and Not less} 1-3 Ethylindene homologs than 212 Xylene (o-. m-. and

-lsomers) 138-142 thylbenzenc 136.2} 17-10 lsopropylbenzene 152.5 E yl l n m-. and l58-|64.6 18-7 p-lsomers) n-Propylbenzene 159.6 l-0.1 Trimethylbenzcne 1.3.5: 1.2.4- and 1.2.3-lsomers) l64.6l76.5 25-6 lndane 177 9-1 Methylindanc homologs 182-203 Dimethyl and Ethyl- Not less indane homologs than 200 2-0.5 Naphthalene 218 Dicyclopentadiene *1 170 0.2-3 Undetected Component *2 140-220 0.7-5.4

NOTE 1 There is a case in which a part or whole of the Llicyelopentadiene is depolymerized by heating to produce cyclopentadiene.

NOTE 2: A part of the undetected component contains cyclopentadiene-methylcyplopentadiene (Jo-dimer and methylcyclopentadiene dimer. There is a case in which a part or whole thereof is depolymerized by heating to produce cyclopentadiene and methyl-eyelopentadiene. and it is possible to analyze these monomers by the above described gas chromatography.

1n the above mentioned components, the total of styrene and its derivatives, indene and its derivatives is -tate of Conjugated Uiolefin C ntent considered as the polymerizable component. Furthermore, in case cyclopentadiene and methylcyclopentadiene are produced by heating and contained in the raw material oil as described in Notes 1 and 2 of Table 1, these monomers are also considered as polymerizable components.

' conjugated diolefin defined in the following equation (1) is adjusted to 3 percent or less.

Conjugated niolcfin C ntent ('1) in the raction 1 (wt. 1) X ("0) lolymertzablc (.or'nonent 1n the racti n I lwt. T) (1) under the following conditions.

5 6- dene defined in the following equation (2) is adjusted above determined condition from a cracked fraction to 8 percent or less. having a boiling range of from l40220 C.

Content o indene and its \llq'l late of indene llerivriti ves in the raction l .-'1.L' Content I L- 1) P lyr eri :arIe C onent in the racti n l. (tit. I In order to concurrently produce a hydrocarbon One example of the separation process employed in resin having a good weather resistance and heat resisthe present invention will be described hereinbelow in tance with a high softening point type hydrocarbon connection with the accompanying drawing, but it is to resin having a softening point of 160 C. and above in be noted that the present invention is not limited to the process according to this invention, it is an essential these separation processes.

condition that the fraction having a boiling point within the range of l40-220 C. is separated by the series of operations into the fractions I and II satisfying the following conditions, respectively, and that each fraction is employed as a raw material oil.

FIGS. 1 and 2 are flow diagrams showing examples of processes for preparing the raw material oil used in the process according to the present invention, respectively.

The separation process of the process according to 1' The fraction 1 this invention will be described by showing two exama. The total content of cyclopentadiene and methylm FIGS- 1 and 'F refefence cllflmcter F cyclopentadiene that is, the Content of conjugated designates a cracl ed Oll fraction having a bollmgrange olefin in the fraction I separated from the above menof from 140 used as a Stamng raw mammal tioned starting raw material oil is adjusted to a value of I and I] desigjate the frficftlonns I Satisfying the 0.7 weight percent or less and the rate of content of the above determined conditions, respectively. Reference conjugated (olefin defined in thg equation (I) is ad character indicates a lighter fraction than the fracjusted to 3 percent or less tion I, particularly, cyclopentadiene and methylcyclob. The total content of indene and its alkyl derivapenjadlene ffacnon (herem'flftffr referred to P Y tives in the fraction I separated from the above men- Conlugated dlolefimand mdlcates a heavier Colored tioned starting raw material oil is adjusted to a value of compoljem than the fractlon n and Produced in the 2 weight percent or less and the rate of content of in- Sepamnon Process as dene defined in the equation (2) is adjusted to 8 per- In FIG. I, the starting raw material oil F is charged cent or less. into a fractionator A-l through line 1, and the fraction- 2. The fraction II ator A-l, can be operated at atmospheric or reduced a. The total content of indene and its alkyl derivatives pressure. In the tower A-l an operation for adjusting in the fraction II separated from the above mentioned the content of indene and its alkyl derivatives to less starting raw material oil is adjusted to a value of not less than 2 weight percent which is one of the determined than 20 weight percent and the rate of content of inconditions for the fraction I is simultaneously carried dene defined in the following equation (3) is adjusted out with another operation for adjusting the content of to not less than 30 percent. indene and its alkyl derivatives to 20 weight percent or Content of indene and its .tllay'l late of Indene Derivatives in the Fraction II (wt. 1.) x 11m Content (5) Polymerlzable Com onent in fire Fraction II (wt. (3)

Each component of the starting raw material oil, of more which is one of the determined conditions for the the fractions I and II is analyzed by gas chromatography fraction II.

A product corresponding to the fraction I is distilled from the top of the tower A-l through line 2. In case 0.7 weight percent or more of the conjugated diolefin is contained in the starting raw material oil or the content of the conjugated diolefin in the distillate oil of the i. Styrene, allylbenzene, 1,3,5-trimethylbenzene, and o-ethyltoluene are analyzed under such a condition that temperature is 100 C. and flow rate of helium is 60 cc/min. by employing a column havinga length of 3 m in which Celite (manufactured by Johns Man- A4 b h ville Corp.) containing 20 percent by weight of Apietower ecomes weight percent or more by t e depolymerization of dicylopentadiene or dimer of igg ggz j g g gag g by Assoclated Elecmcal methylcyclopentadiene or codimer of cyclopentadiene and methylcyclopentadiene (hereinafter referred to simply as conjugated diolefin dimer") in the tower A-l, a valve 4 is closed and valve 3 is opened to charge starting raw material oil or the distillate of the tower A-l into tower C-l. Then, the conjugated diolefin L is ii. Each component other than those described in (i) is analyzed under such a condition that temperature is 125 C. and flow rate of cc/min. by employing a column having a length of 3 m in which Celite containing 20 percent by weight of polyethylene glycol 4,000 is fi"ed 60 cause to distill from the top of the tower C-l, while, a The total content of styrene, its alkyl derivatives, infraction in which the content of the conjugated diolefin dene, its alkyl derivatives, cyclopentadiene, and methis adjusted to 0.7 weight percent or less is taken from ylcyclopentadiene analyzed by the above described the bottom of the tower C-1 and the fraction I is obmethod, is considered as a polymerizable component. tained through a line 5.

In the process of this invention, any distillation This operation can be easily carried out, because the method, such as atmospheric distillation,vacuum distilboiling points of cyclopentadiene and methylcyclolation and extractive distillation, may be used for the pentadiene which are conjugated diolefins are 42 C.

separation of the fraction I satisfying the above deterand C., respectively, and because these temperamined condition and the fraction II satisfying also the tures are lower than the initial boiling point of the starting raw material oil. In case the content of the conjugated diolefins in the distillate oil from the top of the tower A-l is 0.7 weight percent or less, the valve 3 is closed and the valve 4 is opened, and as a result, the fraction 1 can be directly obtained through the line 5 without employing tower C-l.

In case a colored substance having a boiling point of 220 C. and above is produced by heating in the tower A-l, a product corresponding to the fraction 11 to be taken from the bottom of the tower A-l is charged into a tower B-l through a line 7 by closing a valve 9 and opening a valve 8, and then, the fraction 11 is obtained from the top of the tower B-l through a line 10, and, a colored substance H is drawn from the bottom of the tower B-l through a line 11. In case the colored substance in the bottom component of the tower A-l is a very small amount and negligible, the valve 8 is closed and the valve 9 is opened, and the fraction 11 may be obtained through the line without employing the tower 8-1.

In order to satisfy all the conditions, that is, the determined condition for the fraction I that the content and the rate of content of the conjugated diolefin are 0.7 weight percent or less and 3 percent or less, respectively, and the content of indene and its alkyl derivatives and the rate of content of indene are 2 weight percent or less and 8 percent or less, respectively, it is necessary that the amount of the polymerizable component is adjusted to the required amount or more by adopting an operation other than those described above. For this purpose, it is necessary to reduce the amount of the colored substance produced from various polymerizable components by heating in the tower A-l. Therefore. it is preferable to shorten the remaining time of the raw material oil in the bottom of the tower A-l or to lower the temperature at the bottom of the tower by vacuum distillation. For example, conditions such that the remaining time of the raw material oil in the bottom of the tower is 0.5 hour or shorter in the case of atmospheric distillation, the residence time is within 1 hour at a temperature of 130 C. at the bottom of the tower in the case of vacuum distillation, and the residence time is not longer than 2 hours at a temperature of 100 C. at the bottom of the tower in the case of vacuum distillation are suitable for carrying out the process according to the present invention.

On the other hand, the operation such that the content of indene and its alkyl derivatives and the rate of content of indene are adjusted to values of not less than weight percent and not less than 30 percent, respectively, can be attained by selecting the distillation conditions in the tower A-l.

In the example of FIG. 2, when 0.5 weight percent or more of the conjugated diolefin is already contained in the starting raw materail oil F, the raw material oil F is charged into a fractionator C-2 through a line 12 and a valve 13. Then, the conjugated diolefins are caused to distill from the top of the fractionator while an oil is drawn off from the bottom of the tower. The thus drawn off oil is charged into a fractionator A-Z through a line 16. When the content of the conjugated diolefin in the raw material oil F is 0.7 weight percent or less, the raw material oil F may be charged into the tower A-2 through a line 12, a valve 14, and a line 16.

In the tower A-2, the oil is separated into the fractions 1 and II, respectively, by the series of operations, and in this case, it is preferable that distillation at reduced pressure is carried out at a temperature of 170 C. and below at the bottom of the tower A-2 in order to satisfy each determined condition of the fractions 1 and 11. The fraction I can be obtained from the top of the tower A-2 through a line 17, the fraction 11 can be obtained from the side of the tower A-2 through a line 18, and the colored substance 11 is taken from the bottom of the tower through a line 19.

In the process exemplified above, the separation of the fractions I and 11 satisfying the above determined conditions, respectively, can be attained by the adoption of the series of operations. Furthermore, in the process of the present invention, separation processes other than those exemplified above may be adopted as long as the separation is carried out by separating operations in which an intermediate fraction is not produced between the fraction 1 and fraction 11.

The fraction 1 and fraction 11 prepared as mentioned above are used as raw materials, respectively, and 0.0l5 weight percent of Friedel-Crafts type catalysts such as boron trifluoride, aluminum chloride, and complex compound of boron trifluoride and phenol, preferably, boron trifluoride, boron trifluoride etherate, and boron trifluoride phenolate is added to each raw material oil, respectively, the resulting mixture is polymerized at a temperature ranging of -30-+60 C. for a period ranging of 10 minutes-15 hours. Then, the catalysts are decomposed and removed with alkalis such as caustic soda and sodium carbonate, if necessary, the thus treated reaction product is washed with water, and further, unreacted oil and low molecular weight polymer are separated from the reaction product by evaporation or distillation. As a result, an aromatic hydrocarbon resin having a softening point of-60-120 C., a bromine value of 15 or less, and excellent weather resistance and thermal resistance can be obtained from the fraction 1, and another high softening point type aromatic hydrocarbon resin having a softening point of C. and above and a bromine value of not more than 30 can be obtained from the fraction 11.

The softening point of the resin is measured in accordance with .llS (Japanese Industrial Standards) K 2531-1960 and weather resistance thereof is measured by the following means. A composition prepared by kneading each component shown in the following Table 2 is applied on a glass plate in a thickness of 5 mil. The thus obtained coated film is dried by leaving it for 7 days as it is, and an accelerated weathering test in which ultraviolet ray carbon arc radiation accompanied by rainfall for 18 minutes by every 102 minutes at a temperature of 63 1: 3 C. is carried out with repsect to the dried film for 160 hours in accordance with a method of HS K 5400-1970. After the test, a film in which the 60 specular gloss (JlS K 5400-1970) is 60 percent or more and yellowness (.118 K 5400-1970) is 0.1 or less, there being no cracking and blistering, and there being substantially no difference between the film before and after the test is considered to have good weather resistance.

TABLE 2 Compounding Ratio of Paint for Test Sample Resin 20.0 weight percent Safflower Oil Modified Alkyd Resin Having Oil Length of 51% Calcium C arbonate TABLE Z-Continued Compounding Ratio of Paint for Test The heat resisting test of the resin is carried out in such a manner that 40 gr. of a sample resin placed in a glass beaker having a volume of 100 cc, heated to a temperature of 200 C. to be molten. the thus molten resin is stirred in the open air, and after hours, the color of the resin is measured (2 gr. of so treated resin is dissolved in cc of benzene, and the color of the mixture is compared with Garnder standard scale in accordance with ASTM D). In this case, when the resin has a value of not more than 4 of color, it is considered to have good heat resistance.

In the process of this invention, a resin obtained by the polymerization, under the above mentioned polymerization conditions, from a raw material in which at lest one limitation value of the four determined limitations for the fraction 1 that the content of the conjugated diolefin and the rate of content of the conjugated diolefin are not more than 0.7 weight percent and 3 percent, respectively, and the content of indene and its alkyl derivatives and the rate of content of indene are not more than 2 weight percent and 8 percent, respectively, is outside the determined limitations has inferior weather resistance and heat resistance, and particularly, the color of the resin becomes very yellowish. Accordingly, such a resin is unsuitable for, for example, traffic paint in which severe weather resistance and heat resistance are required.

On the other hand, in the process according to the present invention, when a raw material having a content of 20 weight percent or less of indene and its alkyl derivatives and a rate of content of percent or less of indene which are outside the determined limitations for the fraction II is employed and is polymerized under the above mentioned polymerization conditons, the resulting resin has a softening point of 160 C. and below. and accordingly, comparing this resin with that having a softening point of 160 C. and above prepared by the process according to this invention, the former resin has a longer setting time and drying time and inferior gloss and abrasion resistance in use as the resin for printing ink.

The characteristic features of the process of the present invention will be described hereinbelow.

1. According to the process of the present invention, an aromatic hydrocarbon usable for the traffic paint having excellent weather resistance and heat resistance can be obtained.

2. According to the process of the present invention, in spite of employing the same raw oil as in a production of publicly known aromatic petroleum resin as its starting raw material oil, two types of highly valuable resins such as weather resistant resin which cannot be attained from publicly known aromatic petroleum resins, and high softening point resin having a softening point of 160 C. and above can be concurrently obtained by separating the fraction I from the fraction II by the series of operation so as to satisfy the above determined conditions and polymerizing these fractions, respectively.

3. Since the separation is carried out by the series of operations so as not to prouduce an intermediate fraction between the fractions 1 and ll, a starting raw material oil can be effectively used and two types of resin having excellent properties can be obtained in a very high yield with respect to the starting raw material oil.

4. In order to obtain a resin having excellent weather resistance which cannot be attained by heretofore publicly known petroluem resins and the high softening point type resin having a softening point as high as C.. it is unnecessary to use additionally an expensive third component besides the condition that a cracked oil fraction having a boiling range of l40220 C. is employed as its starting raw material oil, and accordingly, the process of the present invention is very advantageous from an industrial viewpoint.

5. Since the separation process for the fraction 1 and fraction ll satisfying the above determined conditions can be carried out by a simple operation, for example, distillation, the apparatus required for carrying out the operation may be a simple one and a cost for requiring the production can be reduced.

According to the process of the present invention, the hydrocarbon resin having excellent weather resistance and heat resistance and the high softening point type hydrocarbon resin having a softening point of 160 C. and above can be obtained, and the weather resistant type resin exhibits its characteristic features when it is used for a resin for a melting type traffic paint in which weather resistance and heat resistance are particularly required The compound ratio for the weather resistant resin according to the present invention employed for melting type traffic marking paint is:

Weather Resistant Resin 2449 pans by weight of This invention Malcic Acid Resin 0-14 Plasticizer l-l0 Pigment and Filler 50-75 For the plasticizer, any of those which can plasticize the resin and lower and adjust the viscosity as its molten state of the resin, such as dibutyl phthalate, dioctyl phthalate, alkyd resin, and paraffin wax, may be employed.

For the pigments and fillers, one can use titanium oxide, calcium carbonate, zince white, and quartz sand powder. These compositions can serve as a traffic paint by heating and melting them or mixing them in powdered form. Furthermore, when glass beads are employed. the required amount of the glass beads may be added to the mixture of the above described compounding ratio. On the other hand, when a solvent volatile type traffic marking paint is prepared, a suitable solvent, such as hydrocarbon solvent, may be added to the above mentioned mixture to knead them.

These traffic marking paints prepared as mentioned above are applied on the surface of a road, by heating and melting the paint at a temperature of -220C. in the case of a melting type traffic marking paint and by heating or at a room temperature in the case of a solvent volatile type paint. The traffic marking paint in which the weather resistant resin of this invention is employed has excellent heat resistance. Accordingly, there is no deterioration and discoloring at the time of heating and melting it, and furthermore, since the weather resistance of a coated film with the paint is excellent, there is no discoloring, cracking, and blistering. In addition, durabilities, such as water resistance and abrasion resistance, are also excellent.

The weather resistant resin of the present invention can not only be used for a traffic marking paint, but also in alkyd resin paint and oil varnish. and the resin exhibits its excellent characteristic features in these uses.

When the hydrocarbon resin having a softening point of 160 C. and above and produced concurrently with the above mentioned weather resistant resin by the process of the present invention is used for a printing ink such as offset ink and gravure ink in which particularly rapid drying properties and gloss are required, excellent effects or advantage can be obtained as compared with conventional hydrocarbon resins.

In the case of offset ink, when a part or whole of rosin modified phenol resin heretofore widely employed is replaced by the high softening point resin having a softening point of 160 C. and above, and produced by the process according to this invention, the setting time and drying time of the resulting offset ink can be shortened and the gloss of the resulting printed surface can be increased.

Furthermore, in the case of gravure ink, when a part or whole of limed rosin varnish heretofore commonly used is replaced by the high softening point resin of the present invention, the resulting gravure ink becomes rapid drying and its gloss and abrasion resistance can be elevated.

In the following, several Examples are disclosed in order to clarify the features of the present invention. However, it will be undertsood that these shall be interpreted as illustrative only, not as limitative of the invention.

EXAMPLE 1 A cracked oil fraction F having a boiling point of 140 to 220 C. which was obtained as a by-product of steam cracking of naphtha, was subjected to gas chromatography, and the result thereof was as follows:

Polymerizablc components (wt. 71) 47.8 Content of cyclopentadiene plus methylcyclopentadienc (wt. 7r) Content of indene plus its alkyl derivatives (wt. 71)

Content of dicyclopentadiene (wt. 71) Rate of conjugated diolefin content (71) Rate of indene content I This fraction F was fractionated into two fractions of fraction l and fraction ll by using the towers as shown in FIG. 1. The specifications and the operating conditions of the fractionator A-l, C-1 and B-1 are shown in the following Table 3.

TABLE 3 Each tower A-l, C-1 and 8-1 was provided with a heater on the feed line, with a condenser on the overhead line and with a reboiler at the bottom. Using the set of towers as shown in FIG. 1, the cracked oil fraction F was fed into the tower A-l from the line 1 through a heater (not shown), then the overhead from the tower A-l was cooled and condensed by a condenser (not shown), a part of the overhead taken from the condenser was refluzed into the top of the tower A-1 and the remainder was fed into the tower C-l through the valve 3 and a heater (not shown). Thus, a light oil fraction L and the fraction I were obtained. The fraction from the bottom of the tower A-] was fed into the tower B-l through a heater (not shown) and the valve 8. From the top of the tower B-l, the cooled fraction II was obtained through a condenser (not shown), and from the bottom of said tower, a colored substance H was obtained. The material balance of these fractions obtained by said series of operations and the compositions of the fractions 1 and [I are shown in the following:

Material Balance of Fractions EXAMPLE 2 To the fraction l as obtained in Example 1 was added 0.5 weight percent of boron trifluoride phenol complex as catalyst, and polymerization was carried out for 3 hours at 20 C. Then the product was washed withaqueous solution of sodium hydroxide to remove the catalyst and then washed with water. Further, unreacted oil and low polymer were removed from the product by distillation, and a weather resistant resin l-A was obtained. The yield of the resin I-A to the raw ma- S eciflcations and Operating onditions of Fractionators terial oil fraction I was 39.0 weight percent. the softening point was 105 C. and the bromine value (ASTM D-1158-57T) was 7. Further. said resin was subjected to accelerated weather resistance test for 160 hours and the resultant degree of yellowing was 0.020. that is the yellowing was hardly observed and the condition of the coating film was almost the same as that of before the test.

EXAMPLE 3 COMPARATIVE EXAMPLE 1 The cracked oil fraction F as used in Example 1 was polymerized in the same conditions as Example 2 and Example 3, and obtained a resin F-l having a softening point of 121 C. and a bromine value of 20, and a resin F-2 having a softening point of 132 C. and a bromine value of 23.

In the process of Example 1, the composition of the overhead product of the tower A-] (not passed through the tower C-l) was as follows:

Polymerizahle components (wt. 7:) 43.5 Content of cyclopentadiene plus methylcyclopentadiene (wt. '71) 2.30 Content of indene plus its alkyl derivatives (wt. /1) 0.90 Rate of conjugated diolefin content ("/l) 5.29 Rate of indene content (7: 2.06

The above fraction was polymerized in the same condition as in Example 2 and a resin F-3 having a softening point of 107 C. and a bromine value of 27 was obtained.

And also, conjugated diolefins were removed from the cracked oil fraction F using the tower C-l alone. as shown in FIG. 1. The composition of the bottom product was as follows:

The above fraction was polymerized in the same condition as in Example 2 and obtained a resin F-4 having a softening point of 120C. and a bromine value of 6.

The resins F-l, F-3 and T4 were subjected to the aforementioned accelerated weather resistance tests and the resultant degrees of yellowing were 0.212, 0.201 and 0.204, respectively, which were observed to be considerably yellowish.

EXAMPLE 4 The resin l-A obtained in Example 2 in accordance with the present invention and the resins F-l, F3 and F-4 as obtained in Comparative Example 1 were subjected to the aforementioned heat resistance tests. The results are shown in the following Table 4. I

TABLE 4 Heat Resistance Tests (The numerals indicate the color of resins by the Gardner scale) Test Time Resin (hr. 0 l 2 3 4 5 l-A 1' l l l 2' 2 F-l 3 4 5 6 7 8 F-3 3 4 5 5 6* 7 F-4 2 3 4 4 5 7 As will be understood from the results in Table 4, the heat resistant resin l-A prepared in accordance with the method of the present invention is far superior than the resins F-l, F-3 and F-4 in viewpoints of the color before the tests and the changes of the color during the tests.

Then, traffic marking paints were prepared using these resins according to the following compounding ratios.

Resin (l-A. F-l. F-3 or F-4) 25 wt. 7: Maleic acid resin (acid value: 65.

Softening point: 120 C.) 7 wt. 7: Safilower oil modified alkyd resin (oil length: 70) 4 wt. 71 Dioctyl phthalate (DOP) 2 wt. 71 Pigment 62 wt. 7!

Polymerizable components (wt. '7) 48.0 Each of the above compounds was heated and mixed of Plus well for 2 hours at 180 C then was applied onto a surmethyleyelopentadiene (wt. '71) 0.35 Comm fi d p|us its face of concrete to form a coating film of 0.5 mm 1n "0 derivatives -f thickness. Each coating film was subjected to 160 fa i dmlcfin O 73 hours accelerated weather resistance test, the results Rate of indene content (7.) 20.0 thereof are shown in the following Table 5.

TABLE 5 Accelerated Weather Resistance Test Resins Used F-3 F-4 Tests Degree of lnitial 0.001 0.002 0.002 0.001

Yellowing After 160 hrs. 0.018 0.232 0.212 0.205

Degree Initial 70 71 70 Specular Gloss After 160 hrs. 65 40 38 37 45. 0 Degree Daylight Initial 74 73 74 Apgarent Re ectanee After hrs. 74 65 62 60 Appearance (Cracks. blisters) good crack crack good As shown in Table 5, the traffic marking paint prepared by using the resin l-A of the present invention is superior in the degree of yellowing, and the lowering of the 60 degree specular gloss is very little, that is. the weather resistance of said paint is superior. On the other hand, the results of the traffic marking paints which were prepared by using the resin F-l, F-3 and F-4 were worse, where the raw material oils of the resins F-l, F- F-3 F-4 do not meet one or more of the definitions of the fraction l. i.e.. the conjugated diolefin content, the rate of conjugated diolefin content, the indene and its alkyl derivative content, and the rate of indene content. I

And futher, a traffic marking paint prepared by using the resin l-A of the present invention was compared with a traffic marking paint in the market which contains maleic acid resin. As the result of an immersing test in water for one month, the water resistance of the former was superior and there was not observed any cracks or blister. On the other hand, occurrence of cracks was observed in the latter.

EXAMPLE 5 Two kinds of offset printing ink were prepared by using the high softening point resin ll-A as obtained in Example 3 and the resin F-2 as obtained in Comparative Example 1. The compositions of the inks were as follows:

Compiisition Composition Resin ll-A 32 Resin F-2 32 Rosin Modified Phenol Resin l5 l5 Linseed Oil 22 22 Hydrocarbon Solvent for Inks 3l 3] The above compositions were fused at 200 C. to obtain varnishes, and pigment and metallic drier were added and kneaded further to prepare offset printing inks. The inks were applied onto art paper by a test printer and were subjected to the tests of drying times and glosses, the test results are shown in the following Table 6.

TABLE 6 Printing Tests TABLE 6-Continued Printing Tests Yellow & Red

Double lmprint 73.0 59.0

As clearly shown in Table 6, in the case of the offset printing ink prepared by using the high softening point resin of the present invention, the setting time and the drying time are short and the gloss is good as compared with the case in which other hydrocarbon resins are used. Further, it was observed that the setting time and the gloss of the ink prepared from composition I was superior as compared with the offset printing inks on the market which were prepared by using rosin modified phenol resin.

We claim:

1. A paint having excellent weather resistance comprising (a) 0-14 parts by weight of maleic acid resin, (b) l-l0 parts by weight of plasticizer, (c) 50-75 parts by weight of pigment or filler or mixture thereof, and (d) 24-49 parts by weight of an aromatic hydrocarbon resin having excellent weather resistance and heat resistance, a softening point of 60i20 C. and a bromine value of 15 or less produced by the process of separating a hydrocarbon fraction having a boiling point within the range of l40220 C. obtained from the thermal cracking of petroleum, said fraction having a content of conjugated diolefin of 0.7 weight percent or less, a rate of conjugated diolefin of 3 percent or less, a total content of indene and its alkyl derivatives of 2 weight percent or less and a rate of indene content of 8 percent or less; polymerizing said fraction at a temperature from 30 to +60 C. for a period of time from l0 minutes to 15 hours in the presence of a Friedel- Crafts catalyst, and recovering said aromatic hydrocarbon resin thus produced, wherein said rate of conjugated diolfefin content, in percent, is calculated by dividing the weight percent conjugated diolefin content in said fraction by the weight percent of the total polymerizable component in said fraction and multiplying by 100, and wherein said rate of indene content, in percent, is calculated by dividing the weight percent of the content of indene and its alkyl derivatives in the fraction by the weight percent of the total polymerizable component in the fraction and multiplying by 100.

2. The paint of claim 1 wherein said plasticizer is selected from the group consisting of dibutyl phthalate, dioctyl phthalate, alkyd resin and paraffin wax.

3. The paint of claim 1 consisting of said maleic acid resin, dioctyl phthalate, a safflower oil modified alkyd resin, pigment, and said aromatic hydrocarbon resin.

4. The paint of claim 1 comprising 25 weight percent of said aromatic hydrocarbon resin, 7 weight percent of a maleic acid resin, 4 weight percent of a safflower oil modifed alkyd resin, 2 weight percent dioctyl phthalate and 62 weight percent pigment.

5. The paint of claim 1 wherein said aromatic hydrocarbon resin is recovered bydecomposing and removing said catalyst and separating unreactd oils and low polymers from the reaction product.

6. The paint of claim 5 wherein the unreacted oils and low polymers are separated from the re action product by evaporation or distillation.

7. The paint of claim 6 wherein said hydrocarbon fraction is obtained by the steam cracking of petroleum.

8. The paint of claim 1 wherein said hydrocarbon fraction is obtained by the steam cracking of petroleum. 

1. A PAINT HAVING EXCELLENT WEATHER RESISTANCE COMPRISING (A) 0-14 PARTS BY WEIGHT OF MALEIC ACID RESIN, (B) 1-10 PARTS BY WEIGHT OF PLASTICIZER, (C) 50-75 PARTS BY WEIGHT OF PIGMENT OR FILLER OR MIXTURE THEREOF, AND (D) 24-49 PARTS BY WEIGHT OF AN AROMATIC HYDROCARBON RESIN HAVING EXCELLENT WEATHER RESISTANCE AND HEAT RESISTANCE, A SOFTENING POINT OF 60*-120*C. AND A BROMINE VALUE OF 15 OR LESS PRODUCED BY THE PROCESS OF SEPARATING A HYDROCARBON FRACTION HAVING A BOILING POINT WITHIN THE RANGE OF 140*-220*C. OBTAINED FROM THE THERMAL CRACKING OR PETROLEUM, SAID FRACTION HAVING A CONTENT OF CONJUGATED DIOLEFIN OF 0.7 WEIGHT PERCENT OR LESS, A RATE OF CONJUGATED DIOLEFIN OF 3 PERCENT OR LESS, A TOTAL CONTENT OF INDENE AND ITS ALKYL DERIVATIVES OF 2 WEIGHT PERCENT OR LESS AND A RATE OF INDENE CONTENT OF 8 PERCENT OR LESS; POLYMERIZING SAID FRACTION AT A TEMPERATURE FROM -30* TO +60*C. FOR A PERIOD OF TIME FROM 10 MINUTES TO 15 HOURS IN THE PRESENCE OF A FRIEDELCRAFTS CATALYST, AND RECOVERING SAID AROMATIC HYDROCARBON RESIN THUS PRODUCED, WHEREIN SAID RATE CONJUGATED DIOLEFIN CONTENT, IN PERCENT, IS CALCULATED BY DIVIDING THE WEIGHT PERCENT CONJUGATED DIOLEFIN CONTENT IN SAID FRACTION BY THE WEIGHT PERCENT OF THE TOTAL POLYMERIZABLE COMPONENT IN SAID FRACTION AND MULTIPLYING BY 100, AND WHEREIN SAID RATE OF INDENE CONTENT, IN PERCENT, IS CALCULATED BY DIVIDING THE WEIGHT PERCENT OF THE CONTENT OF INDENE AND ITS ALKYL DERIVATIVES IN THE FRACTION BY THE WEIGHT PERCENT OF THE TOTAL POLYMERIZABLE COMPONENT IN THE FRACTION AND MULTIPLYING BY
 100. 2. The paint of claim 1 wherein said plasticizer is selected from the group consisting of dibutyl phthalate, dioctyl phthalate, alkyd resin and paraffin wax.
 3. The paint of claim 1 consisting of said maleic acid resin, dioctyl phthalate, a safflower oil modified alkyd resin, pigment, and said aromatic hydrocarbon resin.
 4. The paint of claim 1 comprising 25 weight percent of said aromatic hydrocarbon resin, 7 weight percent of a maleic acid resin, 4 weight percent of a safflower oil modifed alkyd resin, 2 weight percent dioctyl phthalate and 62 weight percent pigment.
 5. The paint of claim 1 wherein said aromatic hydrocarbon resin is recovered by decomposing and removing said catalyst and separating unreactd oils and low polymers from the reaction product.
 6. The paint of claim 5 wherein the unreacted oils and low polymers are separated from the reaction product by evaporation or distillation.
 7. The paint of claim 6 wherein said hydrocarbon fraction is obtained by the steam cracking of petroleum.
 8. The paint of claim 1 wherein said hydrocarbon fraction is obtained by the steam cracking of petroleum. 